KR100210257B1 - Process for the preparation of nitroguanidine derivatives - Google Patents
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- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
하기 일반식(II)의 화합물을 가수분해하는 것을 포함하는 하기 일반식(I)의 1,3-이치환된 2-니트로구아니딘을 제조하는 신규 방법이 제안된다:A novel method of preparing 1,3-disubstituted 2-nitroguanidine of the general formula (I) comprising hydrolyzing a compound of the general formula (II) is proposed:
상기식에서,In the above formula,
R1은 수소 또는 C1-C4알킬이고;R 1 is hydrogen or C 1 -C 4 alkyl;
R2는 수소, C1-C6알킬, C3-C6시클로알킬 또는 -CH2B의 라디칼이며;R 2 is hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, or a radical of —CH 2 B;
R3는 비치환되거나 또는 치환된 C1-C10알킬, C3-C6시클로알킬, 페닐 또는 벤질이고,R 3 is unsubstituted or substituted C 1 -C 10 alkyl, C 3 -C 6 cycloalkyl, phenyl or benzyl,
A는 1 내지 7개 할로겐 원자를 갖는 C1-C3할로알킬, 시클로프로필, 1 내지 3개의 할로겐의 원자를 갖는 할로시클로프로필, C2-C3알켄일, C2-C3알킨일, 1 내지 4개 할로겐 원자를 갖는 C2-C3할로알켄일 및 C2-C3할로알킨일, 1 내지 7개 할로겐 원자를 갖는 C1-C3할로알콕시, C1-C3알킬티오, 1 내지 7개 할로겐 원자를 갖는 C1-C3할로알킬티오, 알릴옥시, 프로파르길옥시, 알릴티오, 프로파르길티오, 할로알릴옥시, 할로알릴티오, 시아노 및 니트로로 구성된 군으로부터 선정된 1 또는 2개의 치환기 그리고 C1-C3알킬, C1-C3알콕시 및 할로겐으로 구성된 군으로 부터 선정된 1 내지 4개의 치환기를 함유할 수 있는 일-내지 사치환되거나 또는 비치환된 방향족 또는 비-방향족, 일환식 또는 이환식 헤테로고리형 라디칼이고; 또A is C 1 -C 3 haloalkyl having 1 to 7 halogen atoms, cyclopropyl, halocyclopropyl having 1 to 3 halogen atoms, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 haloalkenyl and C 2 -C 3 haloalkynyl having 1 to 4 halogen atoms, C 1 -C 3 haloalkoxy having 1 to 7 halogen atoms, C 1 -C 3 alkylthio, Selected from the group consisting of C 1 -C 3 haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro having 1 to 7 halogen atoms To unsubstituted or unsubstituted aromatics which may contain 1 or 2 substituents and 1 to 4 substituents selected from the group consisting of C 1 -C 3 alkyl, C 1 -C 3 alkoxy and halogen Or a non-aromatic, monocyclic or bicyclic heterocyclic radical; In addition
B는 페닐; 시아노페닐; 니트로페닐; 1 내지 3개의 할로겐 원자를 갖는 할로페닐; C1-C3알킬, 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알킬, C1-C3알콕시 또는 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알콕시에 의해 치환된 페닐; 3-피리딜; 5-티아졸릴; C1-C3알킬, 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알킬, 시클로프로필, 할로시클로프로필, C2-C3알켄일, C2-C3알킨일, C1-C3알콕시, 1 내지 4개의 할로겐 원자를 갖는 C2-C3할로알켄일 및 C2-C3할로알킨일, 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알콕시, C1-C3알킬티오, 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알킬티오, 알릴옥시, 프로파르길옥시, 알릴티오, 프로파르길티오, 할로알릴옥시, 할로알릴티오, 할로겐, 시아노 및 니트로로 구성된 군으로 부터 선정된 1 또는 2개의 치환기에 의해 치환된 5-티아졸릴; 또는 1 내지 7개의 할로겐 원자를 갖는 C1-C3 할로알킬, 시클로프로필, 할로시클로프로필, C2-C3알켄일, C2-C3알킨일, C2-C3할로알켄일 및 1 내지 4개의 할로겐 원자를 갖는 C2-C3할로알킨일, 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알콕시, C1-C3알킬티오, 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알킬티오, 알릴옥시, 프로파르길옥시, 알릴티오, 프로파르길티오, 할로알릴옥시, 할로알릴티오, 시아노 및 니트로로 구성된 군으로 부터 선정된 1 또는 2개의 라디칼에 의해 또는 C1-C3알킬, C1-C3알콕시 및 할로겐으로 구성된 군으로 부터 선정된 1 내지 4개의 라디칼에 의해 치환된 3-피리딜임.B is phenyl; Cyanophenyl; Nitrophenyl; Halophenyl having 1 to 3 halogen atoms; C 1 -C 3 alkyl, 1 to 7 having a halogen atom C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy or 1 to 7 having a halogen atom C 1 -C 3 haloalkoxy, phenyl substituted by ; 3-pyridyl; 5-thiazolyl; C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyclopropyl, halo, cyclopropyl, C 2 -C 3 alkenyl having from 1 to 7 halogen atoms, C 2 -C 3 alkynyl, C 1 -C 3 alkoxy, C 2 -C 3 haloalkenyl and C 2 -C 3 haloalkynyl having 1 to 4 halogen atoms, C 1 -C 3 haloalkoxy having 1 to 7 halogen atoms, C 1 -C 3 Alkylthio, C 1 -C 3 haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro having 1 to 7 halogen atoms 5-thiazolyl substituted by one or two substituents selected from the group consisting of; Or C 1 -C 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 haloalkenyl and 1 to 7 having 1 to 7 halogen atoms C 2 -C 3 haloalkynyl having 4 halogen atoms, C 1 -C 3 haloalkoxy having 1 to 7 halogen atoms, C 1 -C 3 alkylthio, C 1 -having 1 to 7 halogen atoms C 3 haloalkylthio, allyloxy, propargyl oxy, allyl thioether, propargyl alkylthio, halo allyloxy, halo-allyl-alkylthio, cyano and nitro by one or two radicals selected from the group as consisting of or C 3-pyridyl substituted by 1 to 4 radicals selected from the group consisting of 1 -C 3 alkyl, C 1 -C 3 alkoxy and halogen.
일반식(I)의 화합물은 농약을 제조하기 위한 중간체로 적합하다.Compounds of formula (I) are suitable as intermediates for the preparation of pesticides.
Description
본 발명은 치환된 2-니트로구아니딘 유도체의 신규 제조 방법에 관한 것이다.The present invention relates to a novel process for the preparation of substituted 2-nitroguanidine derivatives.
1,3-이치환된 2-니트로구아니딘의 제조에 있어서 다른 치환기가 일치환된 2-니트로구아니딘에 더 치환될 수 있다(예컨대 알킬화반응에 의해)는 것은 이미 공지되어있다.(참조: 예컨대 유럽 특허출원 0.375.907호, 동 제 0.376.279호 및 동 제 0.383.091호). 이들 반응에서 출발 물질로 사용된 일치환된 2-니트로구아니딘에는 3개의 반응성 수소 원자가 존재하기 때문에 , 지금까지 제안된 이 유형의 치환 반응은 종종 비선택적으로 실행되어 바람직하지 않은 치환 생성물의 원인이 되었다. 상술한 유럽 특허원에는, 일치환된 니트로이소티오우레아를 메르캅탄을 제거하면서 일차 아민과 반응시키는 것에 의해 1,3-이치환된 2-니트로구아니딘을 제조하는 것이 기재되어 있다. 그러나 알킬티오 이탈기를 함유하고 또 상기 공지 공정에서 출발 화합물로 제안된 니트로이소티오우레아 화합물은 구입하기가 어렵다.In the preparation of 1,3-disubstituted 2-nitroguanidine it is already known that other substituents may be further substituted by mono-substituted 2-nitroguanidine (eg by alkylation) (see eg European Patents). Application 0.375.907, 0.376.279 and 0.383.091). Because of the presence of three reactive hydrogen atoms in the monosubstituted 2-nitroguanidines used as starting materials in these reactions, this type of substitution reaction, which has been proposed thus far, is often performed non-selectively, causing undesirable substitution products. . The aforementioned European patent application describes the preparation of 1,3-disubstituted 2-nitroguanidine by reacting monosubstituted nitroisothioureas with primary amines while removing mercaptans. However, nitroisothiourea compounds containing alkylthio leaving groups and proposed as starting compounds in the above known processes are difficult to purchase.
본 발명의 목적은 바람직하지 않은 부 생성물을 다량 형성함 없이 제어된 방식으로, 1,3-이치환을 허용하는, 용이하게 구입할 수 있는 출발 화합물로 부터 일치환 및 1,3-이치환된 2-니트로구아니딘을 제조하는 개선된 방법을 제공하는데 있다.It is an object of the present invention to mono- and 1,3-disubstituted 2-nitros from readily available starting compounds which allow 1,3-disubstitution in a controlled manner, without forming large quantities of undesirable side products. An improved method of making guanidine is provided.
본 발명에 따르면, 하기 일반식(I)의 1,3-이치환 및 일치환된 2-니트로구아니딘을 제조하는 방법은 하기 일반식(II)의 화합물을 가수 분해하는 것으로 구성된다:According to the invention, the process for preparing 1,3-disubstituted and monosubstituted 2-nitroguanidine of the general formula (I) consists of hydrolyzing the compound of the general formula (II):
상기식에서, R1은 수소 또는 C1-C4알킬이고; R2는 수소, C1-C6알킬, C3-C6시클로알킬 또는 -CH2B의 라디칼이며; R3는 비치환되거나 또는 치환된 C1-C10알킬, C3-C6시클로알킬, 페닐 또는 벤질이고,Wherein R 1 is hydrogen or C 1 -C 4 alkyl; R 2 is hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, or a radical of —CH 2 B; R 3 is unsubstituted or substituted C 1 -C 10 alkyl, C 3 -C 6 cycloalkyl, phenyl or benzyl,
A는 1 내지 7개 할로겐 원자를 갖는 C1-C3할로알킬, 시클로프로필, 1 내지 3개의 할로겐 원자를 갖는 할로시클로프로필, C2-C3알켄일, C2-C3알킨일, 1 내지 4개 할로겐 원자를 갖는 C2-C3할로알켄일 및 C2-C3할로알킨일, 1 내지 7개 할로겐 원자를 갖는 C1-C3할로알콕시, C1-C3알킬티오, 1 내지 7개 할로겐 원자를 갖는 C1-C3할로알킬티오, 알릴옥시, 프로파르길옥시, 알릴티오, 프로파르길티오, 할로알릴옥시, 할로알릴티오, 시아노 및 니트로로 구성된 군으로부터 선정된 1 또는 2개의 치환기 그리고 C1-C3알킬, C1-C3알콕시 및 할로겐으로 구성된 군으로 부터 선정된 1 내지 4개의 치환기를 함유할 수 있는 일-내지 사치환되거나 또는 비치환된 방향족 또는 비-방향족, 일환식 또는 이환식 헤테로고리형 라디칼이고; 또A is C 1 -C 3 haloalkyl having 1 to 7 halogen atoms, cyclopropyl, halocyclopropyl having 1 to 3 halogen atoms, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, 1 C 2 -C 3 haloalkenyl and C 2 -C 3 haloalkynyl having 1 to 4 halogen atoms, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio, 1 C 1 -C 3 haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro having from 7 to 7 halogen atoms Mono- to tetra-substituted or unsubstituted aromatics which may contain 1 or 2 substituents and 1 to 4 substituents selected from the group consisting of C 1 -C 3 alkyl, C 1 -C 3 alkoxy and halogen or Non-aromatic, monocyclic or bicyclic heterocyclic radicals; In addition
B는 페닐; 시아노페닐; 니트로페닐; 1 내지 3개의 할로겐 원자를 갖는 할로페닐; C1-C3알킬, 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알킬, C1-C3알콕시 또는 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알콕시에 의해 치환된 페닐; 3-피리딜; 5-티아졸릴; C1-C3알킬, 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알킬, 시클로프로필, 할로시클로프로필, C2-C3알켄일, C2-C3알킨일, C1-C3알콕시, 1 내지 4개의 할로겐 원자를 갖는 C2-C3할로알켄일 및 C2-C3할로알킨일, 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알콕시, C1-C3알킬티오, 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알킬티오, 알릴옥시, 프로파르길옥시, 알릴티오, 프로파르길티오, 할로알릴옥시, 할로알릴티오, 할로겐, 시아노 및 니트로로 구성된 군으로 부터 선정된 1 또는 2개의 치환기에 의해 치환된 5-티아졸릴; 또는 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알킬, 시클로프로필, 할로시클로프로필, C2-C3알켄일, C2-C3알킨일, 1 내지 4개의 할로겐 원자를 갖는 C2-C3할로알켄일 및 C2-C3할로알킨일, 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알콕시, C1-C3알킬티오, 1 내지 7개의 할로겐 원자를 갖는 C1-C3할로알킬티오, 알릴옥시, 프로파르길옥시, 알릴티오, 프로파르길티오, 할로알릴옥시, 할로알릴티오, 시아노 및 니트로로 구성된 군으로 부터 선정된 1 또는 2개의 라디칼에 의해 또는 C1-C3알킬, C1-C3알콕시 및 할로겐으로 구성된 군으로 부터 선정된 1 내지 4개의 라디칼에 의해 치환된 3-피리딜임.B is phenyl; Cyanophenyl; Nitrophenyl; Halophenyl having 1 to 3 halogen atoms; C 1 -C 3 alkyl, 1 to 7 having a halogen atom C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy or 1 to 7 having a halogen atom C 1 -C 3 haloalkoxy, phenyl substituted by ; 3-pyridyl; 5-thiazolyl; C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyclopropyl, halo, cyclopropyl, C 2 -C 3 alkenyl having from 1 to 7 halogen atoms, C 2 -C 3 alkynyl, C 1 -C 3 alkoxy, C 2 -C 3 haloalkenyl and C 2 -C 3 haloalkynyl having 1 to 4 halogen atoms, C 1 -C 3 haloalkoxy having 1 to 7 halogen atoms, C 1 -C 3 Alkylthio, C 1 -C 3 haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro having 1 to 7 halogen atoms 5-thiazolyl substituted by one or two substituents selected from the group consisting of; Or C 1 -C 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 having 1 to 4 halogen atoms -C 3 haloalkenyl and C 2 -C 3 haloalkynyl, C 1 -C 3 haloalkoxy having 1 to 7 halogen atoms, C 1 -C 3 alkylthio, C 1 having 1 to 7 halogen atoms -By 1 or 2 radicals selected from the group consisting of -C 3 haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro or 3-pyridyl substituted by 1 to 4 radicals selected from the group consisting of C 1 -C 3 alkyl, C 1 -C 3 alkoxy and halogen.
본 발명에 따라 제조된 치환된 2-니트로구아니딘은 -N=C(2) 결합에 관한 이중 결합 이성질체 및 이들의 토우토우머 형태(일반식(I), (Ia), (Ib))로서 존재할 수 있다:Substituted 2-nitroguanidines prepared according to the invention exist as double bond isomers for -N = C (2) bonds and their tautomeric forms (formulas (I), (Ia), (Ib)) Can:
따라서 본 발명에 따른 일반식(I)은 상응하는 이중결합 이성질체 및 일반식(Ia) 및 (Ib)에서와 같은 구조가 일반식(I)을 기술하는 방식에 포함된다고 하는 의미로 이해되어질 수 있다.Therefore, the general formula (I) according to the present invention may be understood as meaning that the corresponding double bond isomers and structures such as those in general formulas (Ia) and (Ib) are included in the manner of describing the general formula (I). .
상기 일반식(I) 및 (II)의 정의에서, 각개 일반적 용어의 의미는 다음과 같이 이해되어져야 한다:In the definitions of Formulas (I) and (II) above, the meaning of each generic term should be understood as follows:
치환기인 할로겐 원자는 플루오르와 염소 및 브롬과 요오드이고 플루오르, 염소 및 브롬이 바람직하다. 이경우 할로겐은 독립적인 치환기 또는 다른 치환기 예컨대 할로알킬, 할로알킬티오, 할로알콕시, 할로시클로알킬, 할로알켄일, 할로알킨일, 할로알릴옥시 또는 할로알릴티오의 일부로 이해되어질 수 있다. 치환기인 알킬, 알킬티오, 알켄일, 알킨일 및 알콕시 라디칼은 직쇄 또는 측쇄일 수 있다. 이 유형의 알킬의 예는 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, 이차 부틸 또는 삼차 부틸이다. 적합한 알콕시 라디칼은 메톡시, 에톡시, 프로폭시, 이소프로폭시 또는 부톡시 및 이들의 이성질체이다. 알킬티오는 예컨대 메틸티오, 에틸티오, 이소프로필티오, 프로필티오 또는 이성질 부틸티오이다. 치환기인 알킬, 알콕시, 알켄일, 알킨일 또는 시클로알킬기가 할로겐에 의해 치환되면, 이들은 부분적으로만 할로겐화되거나 또는 과할로겐화될 수 있다. 상기 주어진 정의가 이 경우에서 할로겐, 알킬 및 알콕시에도 적용된다. 이들 기의 알킬 부분의 예는 플루오르, 염소 및/또는 브롬에 의해 일-내지 삼치환된 메틸 예컨대 CHF2또는 CF3; 플루오르, 염소 및/또는 브롬에 의해 일-내지 오치환된 에틸 예컨대 CH2CF3, CF2CF3, CF2CCl3, CF2CHCl2, CF2CHF2, CF2CFCl2, CF2CHBr2, CF2CHClF, CF2CHBrF 또는 CClFCHClF; 플루오르, 염소 및/또는 브롬에 의해 일-내지 칠치환된 프로필 또는 이소프로필 예컨대 CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3또는 CH(CF3)2; 플루오르, 염소 및/또는 브롬에 의해 일-내지 구치환된 부틸 또는 이들의 이성질체 예컨대 CF(CF3)CHFCF3또는 CH2(CF2)2CF3, 2-클로로시클로프로필 또는 2,2-디플루오로시클로프로필, 2,2-디플루오로비닐, 2,2-디클로로비닐, 2-클로로알킬, 2,3-디클로로비닐 또는 2,3-디브로모비닐이다.Halogen atoms as substituents are fluorine and chlorine and bromine and iodine, with fluorine, chlorine and bromine being preferred. Halogen in this case may be understood as part of an independent substituent or other substituents such as haloalkyl, haloalkylthio, haloalkoxy, halocycloalkyl, haloalkenyl, haloalkinyl, haloallyloxy or haloallylthio. Substituent alkyl, alkylthio, alkenyl, alkynyl and alkoxy radicals may be straight or branched chain. Examples of this type of alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl or tertiary butyl. Suitable alkoxy radicals are methoxy, ethoxy, propoxy, isopropoxy or butoxy and their isomers. Alkylthio is for example methylthio, ethylthio, isopropylthio, propylthio or isomeric butylthio. If the substituent alkyl, alkoxy, alkenyl, alkynyl or cycloalkyl groups are substituted by halogen, they may be only partially halogenated or overhalogenated. The definition given above also applies to halogen, alkyl and alkoxy in this case. Examples of alkyl moieties of these groups include methyl mono- to trisubstituted by fluorine, chlorine and / or bromine such as CHF 2 or CF 3 ; Ethyl mono-substituted by fluorine, chlorine and / or bromine such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCl 3 , CF 2 CHCl 2 , CF 2 CHF 2 , CF 2 CFCl 2 , CF 2 CHBr 2 , CF 2 CHClF, CF 2 CHBrF or CClFCHClF; Propyl or isopropyl mono-substituted by fluorine, chlorine and / or bromine such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2 CF 2 CF 3 or CH (CF 3 ) 2 ; Butyl mono-or substituted by fluorine, chlorine and / or bromine or isomers thereof such as CF (CF 3 ) CHFCF 3 or CH 2 (CF 2 ) 2 CF 3 , 2-chlorocyclopropyl or 2,2-di Fluorocyclopropyl, 2,2-difluorovinyl, 2,2-dichlorovinyl, 2-chloroalkyl, 2,3-dichlorovinyl or 2,3-dibromovinyl.
정의된 알킬, 알콕시 또는 시클로알킬기가 다른 치환기에 의해 치환되면, 이들은 수많은 동일하거나 상이한 유형의 치환기에 의해 일- 또는 다중치환될 수 있다. 바람직하게는, 1 또는 2개의 다른 치환기가 치환된 기에 존재한다.If the defined alkyl, alkoxy or cycloalkyl groups are substituted by other substituents, they may be mono- or polysubstituted by a number of identical or different types of substituents. Preferably, one or two other substituents are present in the substituted group.
치환기인 시클로알킬 라디칼은 예컨대 시클로프로필, 시클로부틸, 시클로펜틸 또는 시클로헥실이다. 알켄일 및 알킨일기는 불포화된 탄소-탄소 결합을 함유한다. 전형적인 대표예는 알릴, 메탈릴 또는 프로파르길, 그리고 비닐 및 에틴일이다. 알릴옥시, 프로파르길옥시, 알릴티오 또는 프로파르길티오에 있는 이중 결합 또는 삼중결합은 포화 탄소 원자에 의해 결합 위치로 부터 헤테로 원자(O 또는 S)로 떨어지는 것이 바람직하다.Cycloalkyl radicals which are substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Alkenyl and alkynyl groups contain unsaturated carbon-carbon bonds. Typical representatives are allyl, metalyl or propargyl, and vinyl and ethynyl. The double bond or triple bond in allyloxy, propargyloxy, allylthio or propargylthio is preferably dropped from the bonding position to a hetero atom (O or S) by a saturated carbon atom.
본 발명에 따른 가수 분해 공정은 상압 및 0 내지 120, 바람직하게는 20 내지 80의 온도 및 반응 성분에 불활성인 용매 또는 희석제중에서 산성 가수분해시키는 것에 의해 실행되는 것이 바람직하다. 바람직하게는 수성-산성 매질에서 일반식(II)의 화합물을 가수분해시키지만, HCl 또는 H2SO4와 같은 무기산 및 알킬카르복시산 및 술폰산과 같은 유기산을 산으로 사용할 수도 있다. 적합한 용매는 메탄올, 에탄올 및 프로판올과 같은 알코올 및 특히 물이다. 다른 적합한 용매는 예컨대 테트라히드로푸란 및 디옥산과 같은 에테르 및 반응에 해를 주지 않는 다른 용매이다. 용매는 혼합물로 사용될 수 있다.Hydrolysis process according to the present invention is atmospheric pressure and 0 to 120 , Preferably 20 to 80 It is preferably carried out by acidic hydrolysis in a solvent or diluent that is inert to the temperature of the reaction component and the reaction component. Preferably the compounds of formula (II) are hydrolyzed in an aqueous-acid medium, but inorganic acids such as HCl or H 2 SO 4 and organic acids such as alkylcarboxylic acids and sulfonic acids can also be used as the acid. Suitable solvents are alcohols such as methanol, ethanol and propanol and especially water. Other suitable solvents are ethers such as, for example, tetrahydrofuran and dioxane and other solvents that do not harm the reaction. Solvents can be used in mixtures.
일반식(II)중에서, 라디칼 R3에 대한 적합한 치환기는 알킬, 시클로알킬, 페닐 또는 벤질기, 할로겐 또는 경우에 따라 1개 또는 그 이상의 유기 라디칼일 수 있고 이들은 바람직하게는 C, O 또는 S를 통하여 알킬, 시클로알킬, 페닐 또는 벤질기에 결합된다.In formula (II), suitable substituents for the radical R 3 may be alkyl, cycloalkyl, phenyl or benzyl groups, halogen or optionally one or more organic radicals and these preferably represent C, O or S Through an alkyl, cycloalkyl, phenyl or benzyl group.
본 발명에 따른 고정을 실행하기 위하여, R3이 C1-C10알킬; C3-C6시클로알킬; 할로겐, 히드록시, C1-C4알콕시, 1 내지 9개 할로겐 원자를 갖는 C1-C4할로알콕시, 디(C1-C4알킬)아미노 및 C1-C5알콕시카르보닐로 구성된 군으로 부터 선정된 1 내지 12개의 라디칼에 의해 치환된 C1-C10알킬; 1 내지 4개의 C1-C4알킬 라디칼 또는 할로겐 원자에 의해 치환된 C3-C6시클로알킬; 페닐; 벤질; 또는 할로겐, C1-C4알킬, 1 내지 9개의 할로겐 원자를 갖는 C1-C4할로알킬, C1-C4알콕시, 1 내지 9개 할로겐 원자를 갖는 C1-C4할로알콕시, C1-C4알킬티오, 니트로 및 시아노로 구성된 군으로 부터 선정된 1 내지 3개의 고리 치환기에 의해 치환된 페닐 또는 벤질인 일반식(II)의 화합물을 출발물질로 사용하는 것이 바람직하다.In order to effect the fixation according to the invention, R 3 is C 1 -C 10 alkyl; C 3 -C 6 cycloalkyl; Group consisting of halogen, hydroxy, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy having 1 to 9 halogen atoms, di (C 1 -C 4 alkyl) amino and C 1 -C 5 alkoxycarbonyl C 1 -C 10 alkyl substituted by 1 to 12 radicals selected from; C 3 -C 6 cycloalkyl substituted by 1 to 4 C 1 -C 4 alkyl radicals or halogen atoms; Phenyl; benzyl; Or halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl having 1 to 9 halogen atoms, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy having 1 to 9 halogen atoms, C Preference is given to using compounds of the general formula (II) which are phenyl or benzyl substituted by one to three ring substituents selected from the group consisting of 1- C 4 alkylthio, nitro and cyano, as starting materials.
헤테로고리형 라디칼 A가 바람직하게는 불포화되고 또 고리원으로서 탄소원자를 통하여 일반식(I)의 어미 물질에 결합된 일반식(I)의 화합물을 제조하기 위해 본 발명에 따른 방법이 특히 사용된다. 특히 본 발명에 따른 정의 A의 헤테로고리는 하기 구조의 어미 기에서 발견된다:The process according to the invention is used in particular for preparing compounds of formula (I) in which the heterocyclic radical A is preferably unsaturated and is bonded to the parent material of formula (I) via a carbon atom as ring member. In particular, the heterocycles of definition A according to the invention are found in the following groups of structures:
상기식에서, E는 C1-C3알킬이고 또 Y는 수소, C1-C3알킬 또는 시클로프로필이다.Wherein E is C 1 -C 3 alkyl and Y is hydrogen, C 1 -C 3 alkyl or cyclopropyl.
상기 예에서 열거된 헤테로고리 A는 불포화되거나 또는 고리계의 치환가능성에 따라서 일반식(I)하에서 주어진 치환기와 같은 4개 이하의 치환기를 가질 수 있다. 바람직하게는 이들 헤테로고리는 할로겐, C1-C3알킬, 1 내지 7개 할로겐 원자를 갖는 C1-C3할로알킬 및 C1-C3할로알콕시, 및 C1-C3알콕시로 구성된 군으로 부터 선정된 1 내지 3개 치환기를 가질 수 있다. 특히 바람직한 헤테로고리 A는 피리딜 라디칼 또는 티아졸릴 라디칼 예컨대 3-피리딜, 2-할로피리드-5-일, 2,3-디할로피리드-5-일, 2-할로티아졸-4-일, 1-옥소피리드-3-일, 1-옥소-2-할로피리드-5-일 및 1-옥소-2,3-디할로피리드-5-일이다.Heterocycle A listed in the above examples may be unsaturated or have up to four substituents, such as the substituents given under formula (I), depending on the substitution of the ring system. Preferably these heterocycles are composed of halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl and C 1 -C 3 haloalkoxy, and C 1 -C 3 alkoxy having 1 to 7 halogen atoms It may have 1 to 3 substituents selected from. Particularly preferred heterocycles A are pyridyl radicals or thiazolyl radicals such as 3-pyridyl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-halothiazole-4- 1, oxopyrid-3-yl, 1-oxo-2-halopyrid-5-yl and 1-oxo-2,3-dihalopyrid-5-yl.
또한 리다칼 B가 불포화되거나 또는 할로겐, C1-C3알킬, 1 내지 7개의 할로겐 원자를 함유하는 C1-C3할로알킬 및 C1-C3할로알콕시, 및 C1-C3알콕시로 구성된 군으로 부터 선정된 1개 또는 2개의 라디칼에 의해 치환될 수 있는 페닐, 3-피리딜 또는 5-티아졸릴 라디칼인 본 발명에 따른 일반식(I)의 화합물을 바람직하게 제조할 수 있다.Also, Ridakal B is unsaturated or halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl and C 1 -C 3 haloalkoxy containing 1 to 7 halogen atoms, and C 1 -C 3 alkoxy Compounds of the general formula (I) according to the invention which are phenyl, 3-pyridyl or 5-thiazolyl radicals which may be substituted by one or two radicals selected from the group consisting of can be preferably prepared.
본 발명에 따라 제조될 수 일반식(I)의 화합물중에서, R1이 수소이고; R2가 수소, 메틸, 에틸 또는 시클로프로필이며; 또 A가 피리딜, 1-옥소피리딜, 티아졸릴이거나 또는 할로겐, C1-C3알킬, C1-C3할로알킬 및 1 내지 7개의 할로겐 원자를 갖는 C1-C3 할로알콕시 및 C1-C3알콕시로 구성된 군으로 부터 선정된 1 내지 3개의 치환기에 의해 치환된 피리딜, 1-옥소피리딜 또는 티아졸릴인 일반식(I)의 화합물이 특히 중요하다. 이점에서 a) R1이 수소이고, 및/또는 b) R2가 수소, C1-C3알킬 또는 시클로프로필이며, 및/또는 c) A가 2-클로로피리드-5-일 또는 2-클로로티아졸-5-일인 일반식(I)의 화합물의 제조가 중요하다. R2가 메틸인 일반식(I)의 화합물이 생물학적으로 특히 중요하다.Among the compounds of formula (I) which may be prepared according to the invention, R 1 is hydrogen; R 2 is hydrogen, methyl, ethyl or cyclopropyl; Or A is pyridyl, 1-oxopyridyl, thiazolyl or halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl and C 1 -C3 haloalkoxy and C 1 with 1 to 7 halogen atoms Of particular interest is a compound of formula (I), which is pyridyl, 1-oxopyridyl or thiazolyl substituted by one to three substituents selected from the group consisting of -C 3 alkoxy. In this regard a) R 1 is hydrogen and / or b) R 2 is hydrogen, C 1 -C 3 alkyl or cyclopropyl, and / or c) A is 2-chloropyrid-5-yl or 2- Of importance is the preparation of a compound of formula (I) which is chlorothiazol-5-yl. Of particular interest are compounds of formula (I) wherein R 2 is methyl.
본 발명에 따라 제조된 일반식(I)의 화합물은 해출 방제용으로 유용한 활성 물질이고 온혈 동물, 물고기 및 식물에 바람직한 허용성을 갖는다. 특히 일반식(I)의 화합물은 농업에서 작물 및 관상용 식물, 특히 목화작물, 채소 및 과일, 숲에서, 물질의 보존 및 보호분야 및 위생분야, 특히 가축 및 생산성 가축에서 생기는 곤충과 절지 동물들을 방제하기에 적합하다. 이들 화합물은 식물에 해로운 흡충, 특히 진디 및 메뚜기에 대하여 매우 효과적이다. 농약 활성을 갖는 본 발명에 따라 제조된 이 유형의 치환된 2-니트로구아니딘은 유럽 특허원 제 376.279호, 동 제 375.907호 및 제 383.091호에 기재되어 있다.Compounds of formula (I) prepared according to the invention are active substances useful for the control of dissolution and have favorable tolerance to warm-blooded animals, fish and plants. In particular, compounds of general formula (I) control insects and arthropods arising from crops and ornamental plants in agriculture, especially cotton crops, vegetables and fruits, forests, conservation and protection of materials and sanitation, in particular livestock and productive livestock. Suitable for These compounds are very effective against insects that are harmful to plants, especially aphids and grasshoppers. Substituted 2-nitroguanidines of this type prepared according to the invention with agrochemical activity are described in European Patent Application Nos. 376.279, 375.907 and 383.091.
본 발명에 따른 방법에 대한 일반식(II) 및 (V)의 출발 화합물 또는 중간체는 신규한 2-니트로이미노-1,3,5-트리아자시클로헥산 유도체이다. 일반식(II) 및 (V)의 중간체를 제조하기 위한 상술한 방법도 본 발명의 일부이다.Starting compounds or intermediates of general formulas (II) and (V) for the process according to the invention are novel 2-nitroimino-1,3,5-triazacyclohexane derivatives. The aforementioned method for preparing intermediates of formulas (II) and (V) is also part of the present invention.
일반식(II)의 화합물은 a) 하기 일반식(III)의 화합물을 포름알데히드, 또는 파라포름알데히드, 및 하기 일반식(IV)의 화합물과 반응시키고, 또 b) 생성한 하기 일반식(IV)의 화합물을 하기 일반식(VI)의 화합물과 반응시키는 것에 의해 제조할 수 있다:The compound of formula (II) comprises a) reacting a compound of formula (III) with formaldehyde or paraformaldehyde and a compound of formula (IV) below, and b) producing the following formula (IV) Can be prepared by reacting a compound of Formula I with a compound of Formula (VI):
상기식에서, 라디칼 R1, R2, R3및 A는 상기에 주어진 의미를 가지고 또 X는 이탈기임.Wherein the radicals R 1 , R 2 , R 3 and A have the meanings given above and X is a leaving group.
기술된 과정의 내용에서 이탈기 X의 예는 다음과 같다: 할로겐, 바람직하게는 염소, 브롬 또는 요오드, 또는 알킬술폰산 라디칼, 메실레이트 또는 토실레이트와 같은 술폰산 라디칼.Examples of leaving groups X in the context of the described process are: halogen, preferably chlorine, bromine or iodine, or sulfonic acid radicals such as alkylsulfonic acid radicals, mesylates or tosylates.
일반식(II)의 화합물을 제조하기 위한 상술한 방법 단계 a)는 불활성 용매중 및 0내지 +140, 바람직하게는 +20내지 +120의 온도에서, 상압, 경우에 따라 승압에서 실행하는 것이 유리하다. 적합한 용매는 특히 메탄올, 에탄올 및 프로판을과 같은 알코올뿐만 아니라 물이다. 다른 적합한 용매는 벤젠, 톨루엔 및 크실렌과 같은 방향족 탄화수소; 테트라히드로푸란, 디옥산 및 디에틸에테르와 같은 에테르; 염화 메틸렌, 클로로포름, 사염화 탄소 및 클로로벤젠과 같은 할로겐화된 탄화수소; 및 반응에 해를주지 않는 다른 용매이다. 용매는 또한 혼합물로도 사용될 수 있다. 경우에 따라서 상기 반응은 HCl, H2SO4또는 술폰산 예컨대 p-톨루엔술폰산과 같은 산 촉매를 부가하면서 실행할 수 있다. 형성된 반응수는 물 분리수를 이용하거나 또는 분자체를 부가하여 적당하게 제거할 수 있다. 상술한 방법단계 b)는 상압 또는 약간 상승된 압력 및 바람직하게는 비양성자성 용매 또는 희석제 존재하에서 실행할 수 있다. 적합한 용매 또는 희석제는 디에틸 에테르, 디프로필 에테르, 디부틸 에테르, 디옥산, 디메톡시에테르 및 테트라히드로푸란과 같은 에테르 및 에테르 유사 화합물; 지방족, 방향족 및 할로겐화된 탄화수소 특히 벤젠, 톨루엔, 크실렌, 클로로포름, 염화 메틸렌, 사염화 탄소 및 클로로벤젠; 니트릴 예컨대 아세토니트릴 또는 프로피오니트릴; 디메틸 술폭사이드 또는 디메틸포름아미드 및 이들 용매의 혼합물이다. 이 방법 단계는 대체로 -20 내지 +140, 바람직하게는 0 내지 +120의 온도에서 바람직하게는 염기 존재하에서 실행될 수 있다. 적합한 염기는 예컨대 탄산 나트륨 및 탄산 칼륨과 같은 탄산염이다. 수소화 나트륨, 수소화 칼륨 및 수소화 칼슘과 같은 수소화물도 염기로 사용될 수 있다. 상기 반응은 염화 세슘과 같은 촉매 존재하에서 실행될 수 있다.The process step a) described above for preparing the compound of formula (II) is carried out in an inert solvent and at zero To +140 , Preferably +20 To +120 At temperatures of, it is advantageous to run at atmospheric pressure and, optionally, elevated pressure. Suitable solvents are in particular water as well as alcohols such as methanol, ethanol and propane. Other suitable solvents include aromatic hydrocarbons such as benzene, toluene and xylene; Ethers such as tetrahydrofuran, dioxane and diethyl ether; Halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; And other solvents that do not harm the reaction. Solvents can also be used in mixtures. In some cases the reaction can be carried out with addition of an acid catalyst such as HCl, H 2 SO 4 or sulfonic acids such as p-toluenesulfonic acid. The reaction water formed can be suitably removed by using water separation water or by adding molecular sieve. The process step b) described above can be carried out at atmospheric or slightly elevated pressure and preferably in the presence of an aprotic solvent or diluent. Suitable solvents or diluents include ethers and ether like compounds such as diethyl ether, dipropyl ether, dibutyl ether, dioxane, dimethoxyether and tetrahydrofuran; Aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachloride and chlorobenzene; Nitriles such as acetonitrile or propionitrile; Dimethyl sulfoxide or dimethylformamide and mixtures of these solvents. This method step is usually -20 to +140 , Preferably 0 to +120 It may be carried out at a temperature of preferably in the presence of a base. Suitable bases are, for example, carbonates such as sodium carbonate and potassium carbonate. Hydrides such as sodium hydride, potassium hydride and calcium hydride may also be used as the base. The reaction can be carried out in the presence of a catalyst such as cesium chloride.
상기 일반식(IV) 및 (VI)의 출발 생성물은 공지된 것이고 시판되고 있거나 또는 공지 방법과 유사하게 쉽게 제조될 수 있다. 일반식(III)의 2-니트로구아니딘 출발 생성물은 공지된 것이다; 이들은 적합한 일차 아민과의 반응에 의해 S-메틸-N-니트로이소티오우레아로 부터 제조될 수 있다(참조: US-PS 제 4.804.780호 및 동 제 4.221.802호). S-메틸-N-니트로이소티오우레아는 S-메틸이소티오우레아를 니트로화시켜 양호한 수율로 수득할 수 있다[참조:J.Am.Chem. Soc. 76. 1877(1954)].The starting products of the above formulas (IV) and (VI) are known and commercially available or can be readily prepared analogously to known methods. 2-nitroguanidine starting products of formula (III) are known; They can be prepared from S-methyl-N-nitroisothiourea by reaction with a suitable primary amine (see US Pat. No. 4.804.780 and 4.221.802). S-methyl-N-nitroisothiourea can be obtained in good yield by nitrating S-methylisothiourea. See J. Am. Chem. Soc. 76. 1877 (1954).
[실시예 1]Example 1
[일반식(V)의 중간체의 제조][Production of Intermediate of General Formula (V)]
a) 2-니트로이미노-5-메틸-1,3,5-트리아자시클로헥산의 제조:a) Preparation of 2-nitroimino-5-methyl-1,3,5-triazacyclohexane:
26.0g의 니트로구아니딘, 에탄올중의 8M 메틸아민 용액 31.1, 물중의 37% 포름알데히드 용액 38및 에탄올 100의 혼합물을 50에서 2시간 동안 가열시킨 다음 여과한다. 수득한 결정을 에탄올 20를 사용하여 3회 세척한 다음 건조시킨다. 융점이 173 내지 175인 하기 구조식의 표제 화합물 25.2g을 수득한다.26.0 g nitroguanidine, 8M methylamine solution in ethanol 31.1 37% formaldehyde solution in water 38 And ethanol 100 A mixture of 50 Heated for 2 hours and then filtered. The obtained crystals were ethanol 20 Wash three times with and then dry. Melting Point 173-175 25.2 g of the title compound of formula
b) 1-메틸-2-니트로이미노-5-n-프로필-1,3,5-트리아자시클로헥산의 제조:b) Preparation of 1-methyl-2-nitromino-5-n-propyl-1,3,5-triazacyclohexane:
1-메틸-2-니트로구아니딘 17.1g, n-프로필아민 12.0, 물중의 37% 포름알데히드 용액 22.0및 에탄올 40의 혼합물을 50에서 4시간 동안 가열한다. n-프로필아민 7.0및 물중의 37% 포름알데히드 용액 13를 더 부가한다. 50에서 2시간 동안 교반한 후, 반응 혼합물을 진공에서 증발시키고 또 석출된 결정을 에테르와 교반한다. 융점 84 내지 86인 하기 구조식의 표제 화합물 26.9g을 수득한다.1-methyl-2-nitroguanidine 17.1 g, n-propylamine 12.0 37% formaldehyde solution in water 22.0 And ethanol 40 A mixture of 50 Heat for 4 hours. n-propylamine 7.0 And 37% formaldehyde solution in water 13 Add more. 50 After stirring for 2 h at, the reaction mixture is evaporated in vacuo and the precipitated crystals are stirred with ether. Melting point 84-86 26.9 g of the title compound of formula
c) 1-메틸-2-니트로이미노-5-페닐-1,3,5-트리아자시클로헥산의 제조:c) Preparation of 1-methyl-2-nitromino-5-phenyl-1,3,5-triazacyclohexane:
30톨루엔중의 1-메틸-2-니트로구아니딘 2.36g, 아닐린 2.11및 파라포름알데히드 1.80g의 혼합물을 진한 HCl 용액 3방울과 처리한 다음 물분리기중에서 6시간 동안 끓인다. 이 반응 혼합물을 진공에서 증발시키고 또 잔류물로 수득한 조 생성물을 메탄올로 부터 재결정화시킨다. 융점이 169 내지 172인 하기 구조식의 표제 화합물을 수득한다.30 2.36 g of 1-methyl-2-nitroguanidine in toluene, 2.11 anilines And a mixture of 1.80 g of paraformaldehyde with 3 drops of concentrated HCl solution and then boil for 6 hours in a water separator. The reaction mixture is evaporated in vacuo and the crude product obtained as a residue is recrystallized from methanol. Melting Point 169-172 The title compound of formula
표 1에 나타낸 일반식(V)의 하기 화합물은 상술한 방법과 유사하게 처리하여 수득할 수 있다:The following compounds of formula (V) shown in Table 1 can be obtained by treating similarly to the above-mentioned methods:
[실시예 2]Example 2
[일반식(II)의 출발 화합물의 제조][Preparation of Starting Compound of Formula (II)]
a) 1-(2-클로로피리드-5-일메틸)-2-니트로이미노-5-시클로프로필-1,3,5-트리아자시클로헥산의 제조a) Preparation of 1- (2-chloropyrid-5-ylmethyl) -2-nitromino-5-cyclopropyl-1,3,5-triacyclohexane
60의 아세토니트릴중의 2-니트로이미노-5-시클로프로필-1,3,5-트리아자시클로헥산 2.96g, 2-클로로-5-클로로메틸피리딘 2.59g 및 탄산 칼륨 2.43g의 혼합물을 환류하에서 16시간 동안 가열한다. 수득한 반응 혼합물을 여과하고, 그 여액을 진공에서 증발시켜 또 형성된 잔류물을 실리카겔 상에서 디클로로메탄/아세트산 에틸(1:1)을 사용하여 크로마토그래피시킨다. 융점이 125 내지 127인 하기 구조식의 표제 화합물 1.73g을 수득한다.60 A mixture of 2.96 g of 2-nitroimino-5-cyclopropyl-1,3,5-triazacyclohexane, 2.59 g of 2-chloro-5-chloromethylpyridine and 2.43 g of potassium carbonate in acetonitrile of Heat for hours. The resulting reaction mixture is filtered and the filtrate is evaporated in vacuo and the resulting residue is chromatographed on silica gel with dichloromethane / ethyl acetate (1: 1). Melting Point 125 to 127 1.73 g of the title compound of formula
b) 1-(2-클로로피리드-5-일메틸)-2-니트로이미노-3-메틸-5-n-프로필-1,3,5-트라아자시클로헥산의 제조b) Preparation of 1- (2-chloropyrid-5-ylmethyl) -2-nitromino-3-methyl-5-n-propyl-1,3,5-triacyclohexane
150의 디메틸포름아미드중의 1-메틸-2-니트로이미노-5-n-프로필-1,3,5-트라아자시클로헥산 20.1g, 2-클로로-5-클로로메틸피리딘 16.2g, 염화 세슘 0.17g 및 탄산 칼륨 27.7g의 혼합물을 110에서 9시간 동안 가열시킨 다음 셀라이트를 통하여 여과한다. 이 여액을 진공에서 증발시킨다. 수득한 조 생성물을 200의 디클로로메탄중에 용해시키고 또 그 용액을 100의 물과 100의 포화 NaCl 용액으로 세척하며, MgSO4상에서 건조시킨 다음 증발시킨다. 잔류물을 아세트산 에틸로 부터 재결정화시킨다. 융점이 137 내지 138인 하기 일반식의 표제 화합물 17.4g을 수득한다.150 1-methyl-2-nitromino-5-n-propyl-1,3,5-triacyclohexane 20.1 g, 2-chloro-5-chloromethylpyridine 16.2 g, cesium chloride 0.17 g in dimethylformamide And a mixture of 27.7 g of potassium carbonate 110 Heated for 9 hours and filtered through celite. This filtrate is evaporated in vacuo. Obtained crude product 200 In dichloromethane and dilute the solution to 100 100's of water Washed with saturated NaCl solution, dried over MgSO 4 and evaporated. The residue is recrystallized from ethyl acetate. Melting Point 137-138 17.4 g of the title compound of the formula
하기 표 2에 수록한 일반식(II)의 화합물은 상술한 과정과 유사하게 제조한다:The compounds of formula (II) listed in Table 2 below are prepared analogously to the process described above:
[실시예 3]Example 3
[일반식(I)의 화합물의 제조][Production of Compound of General Formula (I)]
a) 1-(2-클로로피리드-5-일메틸)-2-니트로-3-n-프로필구아니딘의 제조:a) Preparation of 1- (2-chloropyrid-5-ylmethyl) -2-nitro-3-n-propylguanidine:
10의 메탄올중의 1-(2-클로로피리드-5-일메틸)-2-니트로이미노-3,5-(디-n-프로필)-1,3,5-트리아자시클로헥산 1.35g, 아세트산 3및 물 2의 용액을 50에서 3일간 가열시킨다. 이 혼합물을 100의 아세트산 에틸에 붓고 또 포화 NaCl, 포화 NaHCO3및 포화 NaCl 용액 50씩을 사용하여 계속하여 세척한다. 분리한 유기 상을 MgSO4상에서 건조시키고 증발시킨다. 잔류물로 수득한 조생성물을 실리카겔 상에서 헥산/아세트산 에틸(1:2)을 사용하여 크로마토그래피시킨다. 융점이 120 내지 123인 하기 일반식의 표제 화합물 0.80g을 수득한다.10 1.35 g of 1- (2-chloropyrid-5-ylmethyl) -2-nitroimino-3,5- (di-n-propyl) -1,3,5-triacyclohexane in methanol 3 And water 2 A solution of 50 Heat for 3 days at. 100 of this mixture Poured into ethyl acetate and saturated NaCl, saturated NaHCO 3 and saturated NaCl solution 50 Continue flushing with a flash. The separated organic phase is dried over MgSO 4 and evaporated. The crude product obtained as a residue is chromatographed on silica gel with hexane / ethyl acetate (1: 2). Melting Point 120-123 0.80 g of the title compound of the formula
b) 1-(2-클로로피리드-5-일메틸)-2-니트로-3-메틸구아니딘의 제조:b) Preparation of 1- (2-chloropyrid-5-ylmethyl) -2-nitro-3-methylguanidine:
26의 메탄올중의 1-(2-클로로피리드-5-일메틸)-2-니트로이미노-3-메틸-5-n-프로필-1,3,5-트리아자시클로헥산 4.25g의 용액을 26의 1N HC1을 사용하여 처리하고 또 실온에서 16시간 동안 교반한다. 이 반응 혼합물을 여과하고, 또 여과에 의해 제거된 결정을 소량의 메탄올로 세척하며 또 건조시킨다. 융점이 148 내지 150인 하기 일반식의 표제 화합물 2.51g을 수득한다.26 4.25 g of a solution of 1- (2-chloropyrid-5-ylmethyl) -2-nitromino-3-methyl-5-n-propyl-1,3,5-triacyclohexane in methanol Treated with 1N HC1 and stirred at room temperature for 16 hours. The reaction mixture is filtered and the crystals removed by filtration are washed with a small amount of methanol and dried. Melting point 148 to 150 2.51 g of the title compound of the following general formula is obtained.
하기 표 3에 나타낸 일반식(I)의 화합물은 상기 방법과 유사한 방식으로 수득할 수 있다:The compounds of formula (I) shown in Table 3 below can be obtained in a manner similar to the above method:
Claims (13)
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| CH3395/90-5 | 1990-10-24 | ||
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| BR9714066B1 (en) * | 1996-12-19 | 2009-01-13 | process for the preparation of thiazole derivatives, as well as intermediates and processes for their preparation. | |
| DE19712411A1 (en) * | 1997-03-25 | 1998-10-01 | Bayer Ag | Process for the preparation of 1,3-disubstituted 2-nitroguanidines |
| US6118007A (en) * | 1997-03-31 | 2000-09-12 | Mitsui Chemicals, Inc. | Preparation process of nitroguanidine derivatives |
| BR9809986A (en) * | 1997-06-09 | 2000-08-01 | Novartis Ag | Process for the preparation of nitroguanidine derivatives |
| KR20010022974A (en) * | 1997-08-18 | 2001-03-26 | 한스 루돌프 하우스, 헨리테 브룬너, 베아트리체 귄터 | Method for producing substituted 2-nitroguanidine derivatives |
| AU741658B2 (en) * | 1997-08-20 | 2001-12-06 | Syngenta Participations Ag | Method of producing substituted 2-nitroguanidine derivatives |
| DE19806469A1 (en) * | 1998-02-17 | 1999-08-19 | Bayer Ag | Preparation of 2-nitroguanidine derivatives useful as insecticides and acaricides |
| KR20010041996A (en) * | 1998-03-19 | 2001-05-25 | 한스 루돌프 하우스, 헨리테 브룬너, 베아트리체 귄터 | Process for the preparation of nitroguanidine derivatives |
| DE19961604A1 (en) | 1999-12-21 | 2001-07-05 | Bayer Ag | Process for the preparation of 1,3-disubstituted 2-nitroguanidines |
| DE10003834A1 (en) * | 2000-01-28 | 2001-08-02 | Nigu Chemie Gmbh | Process for the preparation of 1-methyl-3-nitroguanidine |
| JP2001328983A (en) * | 2000-05-19 | 2001-11-27 | Mitsui Chemicals Inc | Method for producing disubstituted nitroguanidine |
| DE10121652A1 (en) * | 2001-05-03 | 2002-11-07 | Bayer Ag | Process for the preparation of 1,3-disubstituted 2-nitroguanidines |
| DE102004056626A1 (en) * | 2004-11-24 | 2006-06-01 | Bayer Cropscience Ag | Substituted oxyguanidines |
| BRPI1008674A2 (en) | 2009-02-19 | 2015-08-25 | Pioneer Hi Bred Int | Methods of reducing the development of resistant pests. |
| BRPI1013946B1 (en) | 2009-05-03 | 2021-05-18 | Monsanto Technology Llc | SYSTEMS AND PROCESSES TO COMBINE DIFFERENT SEED TYPES |
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| IE960441L (en) * | 1988-12-27 | 1990-06-27 | Takeda Chemical Industries Ltd | Guanidine derivatives, their production and insecticides |
| DK0383091T3 (en) * | 1989-02-13 | 1994-02-07 | Bayer Agrochem Kk | Insecticidal active nitro compounds |
| US4937340A (en) * | 1989-03-07 | 1990-06-26 | Aerojet-General Corporation | High energy insensitive cyclic nitramines |
| JP2610988B2 (en) * | 1989-03-09 | 1997-05-14 | 日本バイエルアグロケム 株式会社 | New heterocyclic compounds and insecticides |
| WO1991001978A1 (en) * | 1989-07-28 | 1991-02-21 | Nippon Soda Co., Ltd. | Triazine derivatives |
| US6187773B1 (en) * | 1989-11-10 | 2001-02-13 | Agro-Kanesho Co., Ltd. | Hexahydrotriazine compounds and insecticides |
| JPH0674249B2 (en) * | 1990-04-05 | 1994-09-21 | アグロカネショウ株式会社 | Method for producing substituted nitroguanidines |
| EP0483055A1 (en) * | 1990-10-05 | 1992-04-29 | Ciba-Geigy Ag | Triazacyclohexane derivatives |
| JPH09101978A (en) * | 1995-10-06 | 1997-04-15 | Matsushita Electric Ind Co Ltd | Layout verifying method |
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| US5245040A (en) | 1993-09-14 |
| EP0483062A3 (en) | 1992-10-28 |
| DE59108200D1 (en) | 1996-10-24 |
| GR3021081T3 (en) | 1996-12-31 |
| EP0483062B1 (en) | 1996-09-18 |
| IL99801A (en) | 1996-07-23 |
| IE74712B1 (en) | 1997-07-30 |
| CA2053954C (en) | 2003-06-03 |
| CA2053954A1 (en) | 1992-04-25 |
| KR920007987A (en) | 1992-05-27 |
| JP3268461B2 (en) | 2002-03-25 |
| TW198724B (en) | 1993-01-21 |
| ES2091899T3 (en) | 1996-11-16 |
| IE913718A1 (en) | 1992-05-22 |
| JPH04330049A (en) | 1992-11-18 |
| EP0483062A2 (en) | 1992-04-29 |
| IL99801A0 (en) | 1992-08-18 |
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